ASTM D8064-2016 6931 Standard Test Method for Elemental Analysis of Soil and Solid Waste by Monochromatic Energy Dispersive X-ray Fluorescence Spectrometry Using Multiple Monochrom.pdf

1、Designation: D8064 16Standard Test Method forElemental Analysis of Soil and Solid Waste byMonochromatic Energy Dispersive X-ray FluorescenceSpectrometry Using Multiple Monochromatic ExcitationBeams1This standard is issued under the fixed designation D8064; the number immediately following the design

2、ation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method is based upon e

3、nergy-dispersive X-rayFluorescence (EDXRF) spectrometry using multiple mono-chromatic excitation beams for detection and quantification ofselected heavy metal elements in soil and related solid waste.1.2 This test method is also known as High Definition X-rayFluorescence (HDXRF) or Multiple Monochro

4、matic BeamEDXRF (MMB-EDXRF).1.3 This test method is applicable to various soil matricesfor the determination of Cr, Ni,As, Cd, Hg, and Pb in the rangeof 1 to 5000 mg/kg, as specified in Table 1 and determined bya ruggedness study using representative samples. The limit ofdetection (LOD) for each ele

5、ment is listed in Table 1. The LODis estimated by measuring a SiO2blank sample (see Table X1.1in Appendix X1).1.4 This test method is applicable to other elements: Sb, Cu,Se, Ag, Tl, Zn, Ba, Au, Co, V, Fe, Mn, Mo, K, Rb, Sn, Sr, andTi.1.5 X-ray NomenclatureThis standard names X-ray linesusing the Si

6、egbahn convention.21.6 UnitsThe values stated in SI units are to be regardedas standard. No other units of measurement are included in thisstandard.1.7 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 st

7、andard 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:3D653 Terminology Relating to Soil, Rock, and ContainedFluidsD4944 Test Method for Field Determination of Water (Mois-ture) C

8、ontent of Soil by the Calcium Carbide Gas PressureTesterD5283 Practice for Generation of Environmental Data Re-lated to Waste Management Activities: Quality Assuranceand Quality Control Planning and ImplementationD5681 Terminology for Waste and Waste ManagementD5847 Practice for Writing Quality Cont

9、rol Specificationsfor Standard Test Methods for Water AnalysisE1169 Practice for Conducting Ruggedness TestsE1727 Practice for Field Collection of Soil Samples forSubsequent Lead DeterminationE2554 Practice for Estimating and Monitoring the Uncer-tainty of Test Results of a Test Method Using Control

10、Chart Techniques2.2 Other Documents:ASTM DS46 X-Ray Emission Wavelengths and Kev Tablesfor Nondiffractive Analysis4ASTM MNL 7 Manual on Presentation of Data and ControlChart Analysis, 8thed.4US EPA Method, Method 6200 Field Portable X-Ray Fluo-rescence Spectrometry for the Determination of Elemental

11、Concentrations in Soil and Sediment51This 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 Nov. 1, 2016. Published November 2016. DOI:10.1520/D8064-16.2Jenkins, R.,

12、Manne, R., Robin, R., and Senemaud, C., “Nomenclature Systemfor X-ray Spectroscopy,” Pure method precision is achieved with a monochromatic beamhaving an energy bandwidth (Full Width Half Maximum) lessthan 15 % relative to the selected energy and containing morethan 95 % flux of the spectrum of the

13、excitation beam which isincident on the sample.3.2.5 multiple monochromatic excitation beams, ntwo ormore monochromatic beams.3.2.6 Rayleigh scattering, nthe elastic scattering of anX-ray photon through its interaction with the bound electronsof an atom; this process is also referred to as coherents

14、cattering.3.3 Acronyms:3.3.1 ARVaccepted reference values3.3.2 EDXRFenergy dispersive X-ray fluorescence3.3.3 FPfundamental parameters3.3.4 HDXRFhigh definition X-ray fluorescence3.3.5 LODlimits of detection3.3.6 MMBmultiple monochromatic beams3.3.7 NDnon-detected3.3.8 RSDrelative standard deviation

15、4. Summary of Test Method4.1 The operating conditions presented in this test methodhave been successfully used in the determination of Cd,As, Cr,Pb, Hg, Sb, Cu, Ni, Se, Ag, Tl, Zn, Ba, Sn, and Au in soil andrelated solid waste.4.2 This technique uses one or more monochromatic exci-tation beams to qu

16、antify elemental concentrations in soil andsolid waste samples. The sample is homogenized to a reason-able degree and positioned in front of an aperture where it isexposed to one or more monochromatic X-ray beams that arefocused by X-ray optics from an X-ray source. A nearbydetector is positioned to

17、 collect fluorescent and backscatteredX rays. The X rays collected by the detector are converted toelectric pulses by a digital pulse processor. A multi-channelanalyzer separates the pulses by X-ray energy, forming themeasurement spectrum. The spectrum is processed by an FPmethod to obtain the analy

18、sis result.4.3 The apparatus is calibrated for each monochromaticbeam and the detector. The calibration may be performed bythe manufacturer or by the user.5. Significance and Use5.1 Elemental species such as Cr, Ni,As, Cd, Hg, and Pb arewidely used in many industrial processes. These elements havebe

19、en identified in many former industrial sites driving the needfor a quick, easy method for testing on-site at trace levels insoil and solid waste matrices.5.2 This method may be used for quantitative determina-tions of Cr, Ni, As, Cd, Hg, and Pb in soil matrices and solidwaste. Typical test time is

20、90 seconds to 15 minutes.6. Interferences6.1 Spectral InterferenceSpectral interferences resultfrom spectral overlaps among the X-ray lines that remainunresolved due to limited energy resolution of the detector. Forinstance, the arsenic (As) K peak directly overlaps the lead(Pb) L peak. The Pb L lin

21、e can be used to account for thisoverlap and theAs K lines can then be resolved from the Pb Loverlap. The actual lines used for any particular element shouldbe such that overlaps are minimized. Reference ASTM DataSeries DS46 for detailed information on potential line overlaps.Interactions of photons

22、 and electrons inside the detector resultin additional peaks in the spectrum known as escape peaks andsum peaks. These peaks can overlap with X-ray lines ofinterest, for example, the sum peak of iron (Fe) K can overlapwith the Pb L peak.6.2 Matrix EffectsMatrix effects, also called interelementeffec

23、ts, exist among all elements as the result of absorption offluorescent X rays (secondary X rays) by atoms in thespecimen. Absorption reduces the apparent sensitivity for theelement. In contrast, the atom that absorbs the X rays may inturn emit a fluorescent X ray, increasing apparent sensitivityfor

24、the second element. Mathematical methods may be used tocompensate for matrix effects. A number of mathematicalcorrection procedures are commonly utilized including full FPtreatments and mathematical models based on influence coef-ficient algorithms.6.3 Physical Matrix EffectsPhysical characteristics

25、 of thesample such as particle size and homogeneity. Effects can beminimized by mixing samples, grinding and sieving them to auniform particle size prior to analysis, or by increasing the areaexposed to the X-ray beam path by rotating the sample duringanalysis.TABLE 1 Limit of Detection (LOD) and Me

26、thod RangeElement LOD (mg/kg) Method Range (mg/kg)Cr 2.3 11 to 500Ni 1.1 5 to 500As 0.2 1 to 2000Cd 0.4 2 to 100Hg 0.4 2 to 100Pb 0.6 3 to 5000D8064 1626.4 Moisture EffectsSoil samples that are in excess of15 % moisture content may introduce error to the analysis.Samples with high moisture content c

27、an be dried in an ovenprior to analysis at less than 150C. If mercury is a targetanalyte, a separate portion of the sample should be driedwithout heating and analyzed on its own. Another option is touse the manufacturers auto-moisture correction for moisturecontent using FP modeling.7. Apparatus7.1

28、EDXRF Spectrometer6, designed for X-ray fluorescenceanalysis using multiple monochromatic excitation beams withan energy dispersive detector and with a design that incorpo-rates at a minimum the following features (unless otherwisespecified):7.1.1 Source of X-ray ExcitationAn X-ray tube with azircon

29、ium, molybdenum, rhodium, palladium, silver target orother suitable target can be used.7.1.2 X-ray OpticsX-ray optical elements capable of ac-cepting X rays from a tube and directing monochromaticbeams on the sample. Two or more X-ray optical elements arenecessary to provide multiple monochromatic b

30、eams. At leastone optical element provides a medium energy monochromaticbeam, and at least one optical element provides a high energymonochromatic beam.7.1.3 Beam Shutter, used to select a monochromatic beam orselect a combination of monochromatic beams.7.1.4 X-ray Detector, with energy resolution 1

31、40 eV fullwidth at half maximum of the manganese (Mn) K line.7.1.5 Digital Pulse Processor and Multi-channelAnalyzerA digital pulse processor for pulse shaping andconditioning, and a multi-channel analyzer for binning thepulses according to X-ray energy.7.1.6 Detector ApertureAn aperture in the beam

32、 pathbetween the sample and the detector to limit the field of viewof the detector.7.2 Analyzer Test Stand, may have the following accesso-ries:7.2.1 Sample Cell Rotator (optional), designed to hold aremovable sample cell.7.2.2 Removable Sample CellAn open ended specimenholder compatible with the ge

33、ometry of the MMB-EDXRFspectrometer and is designed to use replaceable X-ray trans-parent film to hold a soil specimen with a minimum depth of 1cm.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reag

34、ents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.7Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy

35、 ofthe determination.8.2 Calibration Standard(s)At least three homogenousreference materials are required for calibration (see Note 1).The calibration standards should provide (a) concentrations ofCr, Ni,As, Cd, Hg, and Pb at or near background soil level, (b)some or all of concentrations of Cr, Ni,

36、 As, Cd, Hg, and Pb areat low range levels, and (c) some or all of concentrations of Cr,Ni, As, Cd, Hg, and Pb are at high range levels. It isrecommended to use calibration standards that are traceable tostandard reference materials when such materials are available.NOTE 1Additional calibration stan

37、dards may be used for improvedaccuracy.8.3 Calibration Verification Sample(s)At least one ho-mogenous reference material containing Cr, Ni, As, Cd, Hg,and Pb is required for calibration.8.4 Drift Correction Monitors (optional)Due to instabilityof the measurement system, the sensitivity and backgroun

38、d ofthe spectrometer may drift with time. Drift correction monitorsmay be used to compensate for this drift. The optimum driftcorrection monitor samples are permanent materials that arestable with repeated exposure to X rays.8.5 GlovesDisposable gloves are recommended for han-dling reference materia

39、ls and other samples.8.6 Quality Control Sample(s)To ensure the quality of theresults, a quality control (QC) sample is used for establishingand monitoring the stability and precision of an analyticalmeasurement system (see 17.4). If possible, the QC sampleshall be reference material representative

40、of samples typicallyanalyzed. The materials shall be stable under the anticipatedstorage conditions. The QC sample can be a calibrationvalidation sample.8.7 Reference MaterialsHomogenous material with aknown elemental composition. Reference materials are avail-able from commercial sources or may be

41、prepared gravimetri-cally. For purposes of this method, homogenous referencematerials in this test method are soils or sludge, unlessotherwise specified.8.8 Independent Reference Material (IRM)A material ofknown purity and concentration obtained either from theNational Institute of Standards and Tec

42、hnology (NIST) or otherreputable supplier.8.9 Silicon Dioxide Powder (SiO2)For preparing gravi-metric empirical calibration standards (if using calibrationmethod B, see 12.5) and for use as a blank sample to monitorinstrument contamination and sample preparation contamina-tion (see 17.3).6The sole s

43、ource of supply of the apparatus known to the committee at this timeis XOS, Inc., 15 Tech Valley Drive, East Greenbush, NY 12061. If you are aware ofalternative suppliers, please provide this information to ASTM InternationalHeadquarters. Your comments will receive careful consideration at a meeting

44、 of theresponsible technical committee,1which you may attend.7Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, D.C. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, B

45、DH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.D8064 1638.10 Single/Multi-Element Aqueous StandardsAqueousreference material with known elemental composition forpreparing gravimetric empirical calibrat

46、ion standards (if usingcalibration method B or matrix spiked).8.11 X-ray Transparent Thin-FilmUsed as a protectivebarrier between the sample and the analyzer. See Note 2.NOTE 2The user should select a thin film that provides for maximumtransmittance. The thin-film used in the development of this tes

47、t methodwas high-purity 12 m polypropylene film.9. Hazards9.1 Occupational Health and Safety standards for X raysand ionizing radiation shall be observed. Guidelines for safeoperating procedures are also given in current handbooks andpublications from original equipment manufacturers. For moreinform

48、ation see similar handbooks on radiation safety.9.2 Use proper personal protective equipment (PPE) whenhandling contaminated soil and solid waste. Consult chemicalsafety data sheets for recommended PPE.10. Sampling and Test Specimen Preparation10.1 SamplingCollected samples in accordance with Prac-t

49、ice E1727 or similar procedure.10.2 Preparation for Measurement:10.2.1 To ensure a representative sample is used, thoroughlymix the sample in the collection container by stirring, mixing,or kneading. Large agglomerations of soil or solid wasteshould be broken up. If mixing is not possible, take at least fiveportions of the sample when transferring.10.2.2 If sample exceeds 15 % moisture content by wetweight it should be dried. Samples that require drying willappear muddy or have visible excess water. If unable todetermine visibly, use Test Me