1、August 2007DEUTSCHE NORM English price group 17No part of this standard may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 13.030.10; 13.080.10!,z
2、,“9875809www.din.deDDIN EN 15309Characterization of waste and soil Determination of elemental composition by X-ray fluorescenceEnglish version of DIN EN 15309:2007-08Charakterisierung von Abfllen und Bden Bestimmung der elementaren Zusammensetzung durch Rntgenfluoreszenz-AnalyseEnglische Fassung DIN
3、 EN 15309:2007-08www.beuth.deDocument comprises 43 pages10.07DIN EN 15309:2007-08 2 National foreword This standard has been prepared by CEN/TC 292 “Characterization of waste” (Secretariat: NEN, the Netherlands). The preparatory work has been done by Working Group 3 of CEN/TC 292. The responsible Ge
4、rman body involved in its preparation was the Normenausschuss Wasserwesen (Water Practice Standards Committee), Technical Committee NA 119-01-02-02 UA Chemische Verfahren. The DIN Standards corresponding to the International Standards referred to in the EN are as follows: ISO 5725-2:1994 DIN ISO 572
5、5-2:2002-12 ISO 11464 DIN ISO 11464 ISO 11465 DIN ISO 11465 ISO 12980:2000 DIN ISO 12980:2006-05 ISO 14869-2:2002 DIN ISO 14869-2:2003-01 National Annex NA (informative) Bibliography DIN ISO 5725-2:2002-12, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for
6、 the determination of repeatability and reproducibility of a standard measurement method (ISO 5725-2:1994 including Technical Corrigendum 1:2002) DIN ISO 11464, Soil quality Pretreatment of samples for physico-chemical analyses DIN ISO 11465, Soil quality Determination of dry matter and water conten
7、t on a mass basis Gravimetric method DIN ISO 12980:2006-05, Carbonaceous materials used in the production of aluminium Green coke and calcined coke for electrodes Analysis using an X-ray fluorescence method (ISO 12980:2000) DIN ISO 14869-2:2003-01, Soil quality Dissolution for the determination of t
8、otal element content Part 2: Dissolution by alkaline fusion (ISO 14869-2:2002) EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15309May 2007ICS 13.030.10; 13.080.10English VersionCharacterization of waste and soil - Determination of elementalcomposition by X-ray fluorescenceCaractrisation des dche
9、ts et du sol - Dtermination de lacomposition lmentaire par fluorescence XCharakterisierung von Abfllen und Bden - Bestimmungder elementaren Zusammensetzung durchRntgenfluoreszenz-AnalyseThis European Standard was approved by CEN on 22 March 2007.CEN members are bound to comply with the CEN/CENELEC I
10、nternal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the CEN Management Centre or to any CEN me
11、mber.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as theofficial versions.CEN members
12、 are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switz
13、erland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2007 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 1
14、5309:2007: EEN 15309:2007 (E) 2 Contents Page Foreword3 Introduction .4 1 Scope 5 2 Normative references 5 3 Terms and definitions .5 4 Safety remarks .7 5 Principle7 6 Apparatus .7 7 Reagents.8 8 Interferences and sources of error 8 9 Sample preparation .9 9.1 General9 9.2 Drying and determination
15、of dry mass9 9.3 Preparation of pressed pellet .9 9.4 Preparation of fused beads 10 10 Procedure .10 10.1 Analytical measurement conditions 10 10.2 Calibration 11 10.3 Analysis of the samples17 11 Quality control18 11.1 Drift correction procedure 18 11.2 Blank test18 11.3 Reference materials.18 12 C
16、alculation of the result18 13 Test report 19 Annex A (informative) Semi-quantitative screening analysis of waste, sludge and soil samples .20 Annex B (informative) Examples for operational steps of the sample preparation for soil and waste samples23 Annex C (informative) Suggested analytical lines,
17、crystals and operating conditions.29 Annex D (informative) List of reference materials applicable for XRF-analysis.31 Annex E (informative) Validation .32 Bibliography 40 EN 15309:2007 (E) 3 Foreword This document (EN 15309:2007) has been prepared by Technical Committee CEN/TC 292 “Characterization
18、of waste“, the secretariat of which is held by NEN. This document has been prepared in coordination with ISO/TC 190 “Soil quality”. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by November 2007, a
19、nd conflicting national standards shall be withdrawn at the latest by November 2007. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, D
20、enmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom EN 15309:2007 (E) 4 Introduction X-ray fluorescence spectrometr
21、y is a fast and reliable method for the quantitative analysis of the total content of certain elements within different matrices. The quality of the results obtained depends very closely on the type of instrument used, e.g. bench top or high performance, energy dispersive or wavelength dispersive in
22、struments. When selecting a specific instrument several factors have to be considered, such as the matrices to be analyzed, elements to be determined, detection limits required and the measuring time. The quality of the results depends on the element to be determined and on the surrounding matrix. D
23、ue to the wide range of matrix compositions and the lack of suitable reference materials in the case of inhomogeneous matrices like waste, it is generally difficult to set up a calibration with matrix-matched reference materials. Therefore this standard describes two different procedures: a quantita
24、tive analytical procedure for homogeneous solid waste, soil and soil-like material in the normative part. The calibration is based on matrix-matched standards; an XRF screening method for solid and liquid material as waste, sludge and soil in the informative Annex A which provides a total element ch
25、aracterisation at a semi-quantitative level. The calibration is based on matrix-independent calibration curves, previously set up by the manufacturer. EN 15309:2007 (E) 5 1 Scope This European Standard specifies the procedure for a quantitative determination of major and trace element concentrations
26、 in homogeneous solid waste, soil and soil-like material by energy dispersive X-ray fluorescence (EDXRF) spectrometry or wavelength dispersive X-ray fluorescence (WDXRF) spectrometry using a calibration with matrix-matched standards. This European Standard is applicable for the following elements: N
27、a, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, Sn, Sb, Te, I, Cs, Ba, Ta, W, Hg, Tl, Pb, Bi, Th and U. Concentration levels between approximately 0,000 1 % and 100 % can be determined depending on the element and the instrument used. 2 N
28、ormative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 14346, Characterisation of
29、 waste Calculation of dry matter by determination of dry residue or water content EN 15002, Characterisation of waste Preparation of test portions from the laboratory sample EN ISO/IEC 17025, General requirements for the competence of testing and calibration laboratories (ISO/IEC 17025:1999) ISO 114
30、64, Soil quality Pretreatment of samples for physico-chemical analysis ISO 11465, Soil quality Determination of dry matter and water content on a mass basis Gravimetric method 3 Terms and definitions For the purpose of this document, the following terms and definitions apply. NOTE See 13 and 10 for
31、non specified terms. 3.1 absorption edge jump of the mass absorption coefficient at a specific wavelength or energy 3.2 absorption of X-rays loss of intensity of X-rays by an isotropic and homogenous material as described by the Bouger-Lambert law 3.3 analytical line specific characteristic X-ray sp
32、ectral line of the atom or ion of the analyte used for determination of the analyte content 3.4 Bremsstrahlung; continuous radiation electromagnetic radiation produced by the acceleration of a charged particle, such as an electron, when deflected by another charged particle, such as an atomic nucleu
33、s EN 15309:2007 (E) 6 3.5 Compton-line spectral line due to incoherent scattering (Compton-effect) occurring when the incident X-ray photon strike an atom without promoting fluorescence NOTE Energy is lost in the collision and therefore the resulting scattered X-ray photon is of lower energy than th
34、e incident X-ray photon. 3.6 drift correction monitors physically stable samples used to correct for instrumental drift 3.7 emitted sample X-rays radiation emitted by sample consisting of X-ray fluorescence radiation and scattered primary X-rays 3.8 fused bead analyte sample prepared by dissolution
35、in a flux 3.9 liquid sample analyte sample submitted as a solution for direct measurement in the sample cup 3.10 mass absorption coefficient constant describing the fractional decrease in the intensity of a beam of X-radiation as it passes through an absorbing medium, expressed in units of cm2/g. Th
36、e mass absorption coefficient is a function of the wavelength of the absorbed radiation and the atomic number of the absorbing element 3.11 polarised excitation X-ray spectrometer energy dispersive X-ray spectrometer where the excitation is performed by polarised radiation and the emitted X-ray fluo
37、rescence radiation is detected along the direction of polarisation 3.12 powder sample analyte sample submitted as a powder for direct measurement in the sample cup 3.13 precision closeness of agreement of results obtained by applying the method several times under prescribed conditions ISO 5725-2:19
38、94 3.14 pressed pellet analyte sample prepared by pressing milled material into a disk 3.15 primary X-rays X-rays by which the sample is radiated 3.16 quality control sample stable sample with known contents, e.g. certified reference material (CRM) used to monitor instrument and calibration performa
39、nce EN 15309:2007 (E) 7 3.17 X-ray fluorescence radiation emission of characteristic X-rays from a sample that has been bombarded by high-energy X-rays or gamma rays 4 Safety remarks Anyone dealing with waste and sludge analysis has to be aware of the typical risks that this kind of material present
40、s irrespective of the parameter to be determined. Waste and sludge samples may contain hazardous e.g. toxic, reactive, flammable, infectious substances, which could potentially undergo biological and/or chemical reaction. Consequently it is recommended that these samples should be handled with speci
41、al care. The gases that may be produced by microbiological or chemical activity are potentially flammable and will pressurise sealed bottles. Bursting bottles are likely to result in hazardous shrapnel, dust and/or aerosol. National regulations should be followed with respect to all hazards associat
42、ed with this method. The X-ray fluorescence spectrometer shall comply with European and national regulations relevant to radiation protection. The person responsible for managing or supervising the operation of X-ray equipment shall provide evidence of his knowledge of radiation protection according
43、 to national regulations. 5 Principle After a suitable preparation, if necessary, the sample is introduced into a XRF-spectrometer and excited by primary X-rays. The intensities of the secondary fluorescent energy lines specific for each element are measured and the elemental composition of the samp
44、le is determined by reference to previously established calibration graphs or equations and applying corrections for inter-element effects. The calibration equations and inter-element corrections are established using pure reagents and/or series of internal or reference materials providing they meet
45、 all the requirements of the relevant preparation technique. 6 Apparatus 6.1 X-ray fluorescence spectrometer The X-ray fluorescence spectrometer shall be able to analyse the elements according to the scope of this European Standard. The following types of X-ray fluorescence spectrometers are applica
46、ble: energy dispersive X-ray fluorescence (EDXRF) spectrometer that achieves the dispersion of the emitted X-ray fluorescence radiation by an energy dispersive detector; wavelength dispersive X-ray fluorescence (WDXRF) spectrometer that achieves the dispersion of the emitted X-ray fluorescence radia
47、tion by diffraction by a crystal or a synthetic multilayer. The spectrometer consists of a number of components: primary X-ray source, an X-ray tube with a high voltage generator; a sample holder; detector unit including electronic equipment; source modifiers to modify the shape or intensity of the
48、source spectrum or the beam shape (like source filters, secondary targets, polarising targets, collimators, focussing optics etc.). EN 15309:2007 (E) 8 The detector unit is different for WDXRF and for EDXRF spectrometers. WDXRF spectrometers take advantage of the dispersion of the emitted radiation
49、by scattering by a crystal or a synthetic multilayer. The detector does not need to be capable of energy discrimination. EDXRF spectrometers use an energy dispersive detector. Pulses of current from the detector, which are a measure of the energy of the incoming X-rays, are segregated into channels according to energy using a Multi-Channel Analyser (MCA). NOTE 1 The use of a high-energy X-ray tube increases the potential for losses of volatile analytes from samples by heating in the spectrometer during analysis. NOTE 2 Th
