1、BS EN 16171:2016Sludge, treated biowasteand soil Determination ofelements using inductivelycoupled plasma massspectrometry (ICP-MS)BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06BS EN 16171:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implem
2、entation of EN 16171:2016. BSI, as a member of CEN, is obliged to publish EN 16171 as a British Standard. However, attention is drawn to the fact that during the development of this European Standard, the UK committee voted against its approval as a European Standard.The UK committee is concerned th
3、at some of the conditions attached to the validation trials lack clarity.It is also the opinion of the UK committee that validation trials for horizontal methods should include conditions for the preparation and extraction of the original sample.The UK participation in its preparation was entrusted
4、to Technical Committee H/-/4, Environmental Testing Programmes.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.
5、 The British Standards Institution 2016. Published by BSI Standards Limited 2016ISBN 978 0 580 91018 0 ICS 13.030.01; 13.080.10 Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strateg
6、y Committee on 30 November 2016.Amendments/corrigenda issued since publicationDate Text affectedBS EN 16171:2016EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16171 October 2016 ICS 13.030.01; 13.080.10 Supersedes CEN/TS 16171:2012English Version Sludge, treated biowaste and soil - Determinati
7、on of elements using inductively coupled plasma mass spectrometry (ICP-MS) Boues, bio-dchets traits et sols - Dtermination des lments en traces par spectromtrie de masse avec plasma induit par haute frquence (ICP-MS) Schlamm, behandelter Bioabfall und Boden - Bestimmung von Elementen mittels Massens
8、pektrometrie mit induktiv gekoppeltem Plasma (ICP-MS) This European Standard was approved by CEN on 19 March 2016. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any
9、alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language
10、 made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, E
11、stonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. EUROPEAN COMMITTEE FOR ST
12、ANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2016 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16171:2016 EBS EN 16171:2016EN 16171:
13、2016 (E) 2 Contents Page European foreword . 4 Introduction 5 1 Scope 6 2 Normative references 6 3 Principle . 6 4 Interferences 7 4.1 General 7 4.2 Spectral interferences . 7 4.2.1 Isobaric elemental interferences 7 4.2.2 Isobaric molecular and doubly-charged ion interferences . 7 4.2.3 Non-spectra
14、l interferences 7 5 Reagents . 8 6 Apparatus 11 6.1 General requirements 11 6.2 Mass spectrometer 11 6.3 Mass-flow controller . 11 6.4 Nebuliser with variable speed peristaltic pump 11 6.5 Gas supply . 11 6.6 Storage bottles for the stock, standard, calibration and sample solutions. 12 7 Procedure 1
15、2 7.1 Test sample solution . 12 7.2 Test solution 12 7.3 Instrument set-up 12 7.4 Calibration 13 7.4.1 Linear calibration function . 13 7.4.2 Standard addition calibration . 13 7.4.3 Determination of correction factors . 13 7.4.4 Variable isotope ratio . 13 7.5 Sample measurement . 13 8 Calculation
16、14 9 Expression of results . 14 10 Performance characteristics 15 10.1 Blank . 15 10.2 Calibration check . 15 10.3 Internal standard response 15 10.4 Interference . 15 10.5 Recovery 15 10.6 Performance data . 16 11 Test report 16 Annex A (informative) Repeatability and reproducibility data . 17 BS E
17、N 16171:2016EN 16171:2016 (E) 3 Annex B (informative) Selected isotopes and spectral interferences for quadrupole ICP-MS instruments 24 Bibliography . 25 BS EN 16171:2016EN 16171:2016 (E) 4 European foreword This document (EN 16171:2016) has been prepared by Technical Committee CEN/TC 444 “Test meth
18、ods for environmental characterization of solid matrices”, the secretariat of which is held by NEN. 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 April 2017, and conflicting national standards s
19、hall be withdrawn at the latest by April 2017. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document supersedes CEN/TS 16171:2
20、012. The preparation of the previous edition of this analytical method by CEN is based on a mandate by the European Commission (Mandate M/330), which assigned the development of standards on sampling and analytical methods for hygienic and biological parameters as well as inorganic and organic deter
21、minants, aiming to make these standards applicable to sludge, treated biowaste and soil as far as this is technically feasible. This document contains the following technical changes in comparison with the previous edition: repeatability and reproducibility data have been added from a European inter
22、laboratory comparison organized by the German Federal Institute for Materials Research and Testing BAM in 2013 (see Annex A). According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Bel
23、gium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switz
24、erland, Turkey and the United Kingdom. BS EN 16171:2016EN 16171:2016 (E) 5 Introduction This European Standard is applicable and validated for several types of matrices as indicated in Table 1 (see Annex A for the results of validation). Table 1 Matrices for which this European Standard is applicabl
25、e and validated Matrix Materials used for validation Sludge Municipal sludge Biowaste Compost Soil Soil WARNING Persons using this European Standard should be familiar with usual laboratory practice. This European Standard does not purport to address all of the safety problems, if any, associated wi
26、th its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions. IMPORTANT It is absolutely essential that tests conducted according to this European Standard be carried out by suitably trained sta
27、ff. BS EN 16171:2016EN 16171:2016 (E) 6 1 Scope This European Standard specifies a method for the determination of the following elements in aqua regia or nitric acid digests of sludge, treated biowaste and soil: Aluminium (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi),
28、 boron (B), cadmium (Cd), calcium (Ca), cerium (Ce), cesium (Cs), chromium (Cr), cobalt (Co), copper (Cu), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), gallium (Ga), germanium (Ge), gold (Au), hafnium (Hf), holmium (Ho), indium (In), iridium (Ir), iron (Fe), lanthanum (La), lead (Pb
29、), lithium (Li), lutetium (Lu), magnesium (Mg), manganese (Mn), mercury (Hg), molybdenum (Mo), neodymium (Nd), nickel (Ni), palladium (Pd), phosphorus (P), platinum (Pt), potassium (K), praseodymium (Pr), rhenium (Re), rhodium (Rh), rubidium (Rb), ruthenium (Ru), samarium (Sm), scandium (Sc), seleni
30、um (Se), silicon (Si), silver (Ag), sodium (Na), strontium (Sr), sulfur (S), tellurium (Te), terbium (Tb), thallium (Tl), thorium (Th), thulium (Tm), tin (Sn), titanium (Ti), tungsten (W), uranium (U), vanadium (V), ytterbium (Yb), yttrium (Y), zinc (Zn), and zirconium (Zr). The working range depend
31、s on the matrix and the interferences encountered. The method detection limit of the method is between 0,1 mg/kg dry matter and 2,0 mg/kg dry matter for most elements. The limit of detection will be higher in cases where the determination is likely to be interfered (see Clause 4) or in case of memor
32、y effects (see e.g. EN ISO 17294-1:2006, 8.3). The method has been validated for the elements given in Table A.1 (sludge), Table A.2 (compost) and Table A.3 (soil). The method is applicable for the other elements listed above, provided the user has verified the applicability. 2 Normative references
33、The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 1593
34、4, Sludge, treated biowaste, soil and waste Calculation of dry matter fraction after determination of dry residue or water content EN 16173, Sludge, treated biowaste and soil Digestion of nitric acid soluble fractions of elements EN 16174, Sludge, treated biowaste and soil Digestion of aqua regia so
35、luble fractions of elements EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696) EN ISO 17294-1:2006, Water quality Application of inductively coupled plasma mass spectrometry (ICP-MS) Part 1: General guidelines (ISO 17294-1:2004) 3 Principle Digests of sludge,
36、treated biowaste or soil with nitric acid or aqua regia (see EN 16173 and EN 16174) are analysed by ICP-MS to get a multi-elemental determination of analytes. The method measures ions produced by a radio-frequency inductively coupled plasma. Analyte species originating in the digest solution are neb
37、ulised and the resulting aerosol is transported by argon gas into the plasma. The ions produced by the high temperatures of the plasma are entrained in the plasma gas and introduced, by means of an interface, into a mass spectrometer, sorted according to their mass-to-charge ratios and quantified wi
38、th a detector (e.g. channel electron multiplier). BS EN 16171:2016EN 16171:2016 (E) 7 NOTE For the determination of tin only aqua regia extraction applies (EN 16174). 4 Interferences 4.1 General Interferences shall be assessed and valid corrections applied. Interference correction shall include comp
39、ensation for background ions contributed by the plasma gas, reagents, and constituents of the sample matrix. Detailed information on spectral and non-spectral interferences is given in EN ISO 17294-1:2006, Clause 6. 4.2 Spectral interferences 4.2.1 Isobaric elemental interferences Isobaric elemental
40、 interferences are caused by isotopes of different elements of closely matched nominal mass-to-charge ratio and which cannot be separated due to an insufficient resolution of the mass spectrometer in use (e.g. 114Cd and 114Sn). Element interferences from isobars may be corrected by taking into accou
41、nt the influence from the interfering element (see EN ISO 17294-1:2006). The isotopes used for correction shall be free of interference if possible. Correction options are often included in the software supplied with the instrument. Common isobaric interferences are given in Table B.1. 4.2.2 Isobari
42、c molecular and doubly-charged ion interferences Isobaric molecular and doubly-charged ion interferences in ICP-MS are caused by ions consisting of more than one atom or charge, respectively. Examples include 40Ar35Cl+and 40Ca35Cl+ion on the 75As signal or 98Mo16O+ions on the 114Cd+signal. Natural i
43、sotope abundances are available from the literature. The accuracy of correction equations is based upon the constancy of the observed isotopic ratios for the interfering species. Corrections that presume a constant fraction of a molecular ion relative to the “parent“ ion have not been found to be re
44、liable, e.g. oxide levels can vary with operating conditions. If a correction for an oxide ion is based upon the ratio of parent-to-oxide ion intensities, this shall be determined by measuring the interference solution just before the sequence is started. The validity of the correction coefficient s
45、hould be checked at regular intervals within a sequence. Another possibility to remove isobaric molecular interferences is the use of an instrument with collision/reaction cell technology. The use of high resolution ICP-MS allows the resolution of these interferences and additionally double-charged
46、ion interferences. The response of the analyte of interest shall be corrected for the contribution of isobaric molecular and doubly charged interferences if their impact can be higher than three times the detection limit or higher than half the lowest concentration to be reported. More information a
47、bout the use of correction factors is given in EN ISO 17294-1. 4.2.3 Non-spectral interferences Physical interferences are associated with sample nebulisation and transport processes as well as with ion-transmission efficiencies. Nebulisation and transport processes can be affected if a matrix compo
48、nent causes a change in surface tension or viscosity. Changes in matrix composition can cause BS EN 16171:2016EN 16171:2016 (E) 8 significant signal suppression or enhancement. Solids can be deposited on the nebuliser tip of a pneumatic nebuliser and on the cones. It is recommended to keep the level
49、 of total dissolved solids below 0,2 % (2 000 mg/l) to minimise deposition of solids in the sample introduction system of the plasma torch. An internal standard can be used to correct for physical interferences if it is carefully matched to the analyte, so that the two elements are similarly affected by matrix changes. Other possibilities to minimise non-spectral interferences are matrix matching, particularly matching of the acid concentration, and standard addition. When intolerable physical interferences are present in a sample, a significant suppre
