1、BS EN 15309:2007ICS 13.030.10; 13.080.10NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDCharacterizationof waste and soil Determination ofelemental compositionby X-ray fluorescenceThis British Standardwas published under theauthority of the StandardsPolicy and S
2、trategyCommittee on 31 May 2009 BSI 2009ISBN 978 0 580 55631 9Amendments/corrigenda issued since publicationDate CommentsBS EN 15309:2007National forewordThis British Standard is the UK implementation of EN 15309:2007.The UK participation in its preparation was entrusted to TechnicalCommittee B/508/
3、3, Characterization of waste.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contract. Users are responsible for its correct application.Compliance with a British Standard c
4、annot confer immunityfrom legal obligations.BS EN 15309:2007EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15309May 2007ICS 13.030.10; 13.080.10English VersionCharacterization of waste and soil - Determination of elementalcomposition by X-ray fluorescenceCaractrisation des dchets et du sol - Dter
5、mination 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 Internal Regulations
6、 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 member.This European
7、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 are the national s
8、tandards 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, Switzerland and United K
9、ingdom.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 15309:2007: EBS EN 1
10、5309:2007EN 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 of
11、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 Calc
12、ulation 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, cry
13、stals and operating conditions.29 Annex D (informative) List of reference materials applicable for XRF-analysis.31 Annex E (informative) Validation .32 Bibliography 40 BS EN 15309:2007EN 15309:2007 (E) 3 Foreword This document (EN 15309:2007) has been prepared by Technical Committee CEN/TC 292 “Char
14、acterization 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 Nov
15、ember 2007, and 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, Czec
16、h Republic, Denmark, 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 BS EN 15309:2007EN 15309:2007 (E) 4 Introduction X
17、-ray fluorescence spectrometry 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 dispersiv
18、e or wavelength dispersive instruments. 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
19、 on the surrounding matrix. Due 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 dif
20、ferent procedures: a quantitative 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 whic
21、h provides a total element characterisation at a semi-quantitative level. The calibration is based on matrix-independent calibration curves, previously set up by the manufacturer. BS EN 15309:2007EN 15309:2007 (E) 5 1 Scope This European Standard specifies the procedure for a quantitative determinat
22、ion of major and trace element concentrations 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 Standar
23、d is applicable for the following elements: Na, 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 dependin
24、g on the element and the instrument used. 2 Normative 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 amend
25、ments) applies. EN 14346, Characterisation of 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 calibrat
26、ion laboratories (ISO/IEC 17025:1999) ISO 11464, 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 a
27、nd definitions apply. NOTE See 13 and 10 for 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 ana
28、lytical line specific characteristic X-ray spectral 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 anoth
29、er charged particle, such as an atomic nucleus BS EN 15309:2007EN 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 th
30、e resulting scattered X-ray photon is of lower energy than the 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
31、X-rays 3.8 fused bead analyte sample prepared by dissolution 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
32、 through an absorbing medium, expressed in units of cm2/g. The 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 i
33、s performed by polarised radiation and the emitted X-ray fluorescence 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 m
34、ethod several times under prescribed conditions ISO 5725-2:1994 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 mater
35、ial (CRM) used to monitor instrument and calibration performance BS EN 15309:2007EN 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 ana
36、lysis has to be aware of the typical risks that this kind of material presents 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. C
37、onsequently it is recommended that these samples should be handled with special 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.
38、 National regulations should be followed with respect to all hazards associated 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 equipm
39、ent shall provide evidence of his knowledge of radiation protection according 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 spe
40、cific for each element are measured and the elemental composition of the sample 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
41、reagents and/or series of internal or reference materials providing they meet 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
42、Standard. The following types of X-ray fluorescence spectrometers are applicable: 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) spec
43、trometer that achieves the dispersion of the emitted X-ray fluorescence radiation 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 el
44、ectronic equipment; source modifiers to modify the shape or intensity of the source spectrum or the beam shape (like source filters, secondary targets, polarising targets, collimators, focussing optics etc.). BS EN 15309:2007EN 15309:2007 (E) 8 The detector unit is different for WDXRF and for EDXRF
45、spectrometers. WDXRF spectrometers take advantage of the dispersion of the emitted radiation 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 dete
46、ctor, 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
47、 analysis. NOTE 2 The new generation of EDXRF spectrometers takes advantage of the polarising target theory resulting in a significant decrease of the background scattering, and therefore lower limits of detection can be achieved (comparable to WDXRF). 6.2 Mill, preferable with walls made of agate,
48、corundum or zircon. 6.3 Pellet preparation equipment: manual or automatic pellet press, capable of providing a pressure of at least 100 kN. 6.4 Aluminium cup: supporting backing cup for pressed pellets. 6.5 Fusion apparatus: electric, gas or high frequency induction furnace that can be heated up to
49、a fixed temperature of between 1 050 C and 1 250 C. 6.6 Fusion crucibles: crucibles made of non-wetting platinum alloy (Pt 95 %; Au 5 % is suitable). Lids, if used, shall be made from platinum alloy. NOTE Certain metal sulphides (so called platinum poisons) affect the platinum crucibles in which the sample is melted. 6.7 Casting moulds: non-wetting platinum alloy (Pt 95 %; Au 5 % is suitable). 7 Reagents The reagents mentioned are used as carrier material. 7.1 Binder: liquid or solid binder free of analytes of interest. Solid materials can co
